Method for producing isothiocyanate compound having carboxyl group

a technology of isothiocyanate and carboxyl group, which is applied in the field of producing isothiocyanate compound, can solve the problems of high cost of tetramethylthiuram disulfide to be used, inability to synthesize an isothiocyanate having an electron-drawing group, and high toxicity of thiophosgene itself, etc., and achieves high purity, high yield, and simple production.

Inactive Publication Date: 2013-02-05
NISSAN CHEM IND LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0040]According to the present invention, it is possible to provide a novel method whereby without using strongly toxic thiophosgene or expensive tetramethylthiuram disulfide, the corresponding isothiocyanate compound can be produced safely, inexpensively, simply in a high yield and with high purity under mild conditions.

Problems solved by technology

It is generally taken for granted that the method for synthesizing an isothiocyanate from an amino compound and carbon disulfide is suitable for the synthesis of an alkyl isothiocyanate but is inferior in the yield for an aryl isothiocyanate, and that the yield may be improved by using triethylamine as a basic catalyst, but by such a method, it is not possible to synthesize an aryl isothiocyanate having an electron-withdrawing group(s) (e.g. Non-Patent Document 1).
Among them, the method of using thiophosgene has a problem that thiophosgene itself has a very strong toxicity and bad odor.
Further, the method of employing tetramethylthiuram disulfide has a problem that isolation of reaction intermediate is necessary, whereby the operation is cumbersome; the reaction condition is severe such that heating is carried out at a high temperature in the presence of acid; and tetramethylthiuram disulfide to be used is expensive.

Method used

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  • Method for producing isothiocyanate compound having carboxyl group
  • Method for producing isothiocyanate compound having carboxyl group
  • Method for producing isothiocyanate compound having carboxyl group

Examples

Experimental program
Comparison scheme
Effect test

example 1

4-Isothiocyanatobenzoic acid

[0114]Carbon disulfide (0.66 mL, 11 mmol) was added to a mixture comprising 4-aminobenzoic acid (0.50 g, 3.6 mmol), tetrahydrofuran (2.5 mL), water (2.5 mL) and triethylamine (1.3 mL, 9.1 mmol), followed by stirring at room temperature for 24 hours. To the obtained reaction mixture, a tetrahydrofuran (2.5 mL) solution of iodine (1.0 g, 4.0 mmol) was dropwise added over a period of 5 minutes at 0° C., followed by stirring at 0° C. for further two hours. Thereafter, 1M hydrochloric acid (3.6 mL) and sodium sulfite (91 mg, 0.72 mmol) were added and stirred. Then, ethyl acetate (15 mL) was added, and the organic layer was separated and concentrated under reduced pressure to dryness. To the residue, ethyl acetate (5 mL) and hexane (5 mL) were added and thoroughly mixed, and then, the insoluble matter was collected by filtration to obtain 4-isothiocyanatobenzoic acid as a colorless solid (0.65 g, yield: 100%, HPLC purity: 92%, HPLC retention time: 3.7 min). LC-...

example 2

3-Isothiocyanatobenzoic acid

[0117]Carbon disulfide (0.26 mL, 4.4 mmol) was added to a mixture comprising 3-aminobenzoic acid (0.20 g, 1.5 mmol), tetrahydrofuran (1.0 mL), water (1.0 mL) and triethylamine (0.51 mL, 3.6 mmol), followed by stirring at room temperature for 24 hours. To the obtained reaction mixture, a tetrahydrofuran (1.0 mL) solution of iodine (0.41 g, 1.6 mmol) was dropwise added over a period of 5 minutes at 0° C., followed by stirring at 0° C. for further two hours. Thereafter, 1M hydrochloric acid (1.5 mL) and sodium sulfite (38 mg, 0.30 mmol) were added and mixed. Then, ethyl acetate (6 mL) was added, and the organic layer was separated and concentrated under reduced pressure to dryness. To the residue, ethyl acetate (4 mL) and water (2 mL) were added, and the organic layer was concentrated under reduced pressure to dryness to obtain 3-isothiocyanatobenzoic acid as a cream-colored solid (0.25 g, yield: 96%, HPLC purity: 95%, HPLC retention time: 3.6 min). LC-MS ES...

example 3

4-Isothiocyanato-2-chlorobenzoic acid

[0118]Carbon disulfide (0.26 mL, 4.4 mmol) was added to a mixture comprising 4-amino-2-chlorobenzoic acid (0.26 g, 1.5 mmol), tetrahydrofuran (1.0 mL), water (1.0 mL) and triethylamine (0.51 mL, 3.6 mmol), followed by stirring at room temperature for 24.5 hours. To the obtained reaction mixture, a tetrahydrofuran (1.0 mL) solution of iodine (0.41 g, 1.6 mmol) was dropwise added over a period of 5 minutes at 0° C., followed by stirring at 0° C. for further two hours. Thereafter, 1M hydrochloric acid (1.5 mL) and sodium sulfite (38 mg, 0.30 mmol) were added and stirred. Then, ethyl acetate (6 mL) was added, and the organic layer was separated and concentrated under reduced pressure to dryness. To the residue, water (4 mL) and sodium hydrogencarbonate (0.14 g, 1.7 mmol) were added, and the insoluble matter was removed by filtration. To the filtrate, 1M hydrochloric acid (1.5 mL) and water (2.0 mL) were added, and the precipitated solid was collected...

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Abstract

To provide a novel method for producing an isothiocyanate compound having a carboxyl group(s) from the corresponding amino compound having a carboxyl group(s).A method for producing an isothiocyanate compound which has a carboxyl group(s) and is represented by the formula (2). And the method comprises reacting an amino compound which has a carboxyl group(s) and is represented by the formula (1) (wherein A is e.g. a C6-14 aromatic hydrocarbon group or a C1-12 saturated hydrocarbon group, and B is e.g. a single bond, a C6-14 aromatic hydrocarbon group or a C1-12 saturated hydrocarbon group), in a solvent, with carbon disulfide (CS2) and then with a halogen as a simple substance.

Description

TECHNICAL FIELD[0001]The present invention relates to a method for producing an isothiocyanate compound having the carboxyl group(s) from the corresponding amino compound having a carboxyl group(s).BACKGROUND ART[0002]An isothiocyanate group is a very useful functional group in synthetic organic chemistry since its reactivity is high and it can be led to various chemical structures. And, a carboxyl group is a useful functional group in the field of organic materials, drugs or agricultural chemicals because of its characteristic acidity and hydrogen bonding ability. Accordingly, an isothiocyanate compound having a carboxyl group(s), which has such two functional groups in one molecule, can be said to be a very useful compound as a product or a synthetic intermediate in the field of organic materials, drugs or agricultural chemicals. As an example, it is known that 3,5-diisothiocyanatobenzoic acid is useful as a starting material for the synthesis of a metal-binding polypeptide (e.g. ...

Claims

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Application Information

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Patent Type & Authority Patents(United States)
IPC IPC(8): C07C331/28C07C331/30C07C331/20
CPCC07C331/20C07C331/24C07C331/30C07C331/28C07C2101/14C07C2601/14
Inventor NAKANO, SATOSHISAITO, DAISUKE
Owner NISSAN CHEM IND LTD
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